Novel 3-sulfinatomethyl-or 3-sulfonatomethyl-4-sulfomethyl pyrrolidinium betaines and their salts as well as process for making the same

Abstract

Novel 3-sulfinatomethyl or 3-sulfonatomethyl-4-sulfomethyl-pyrrolidinium betaines are disclosed which have the formula <IMAGE> These novel compounds are obtained by reacting diallyl-triallyl ammonium salts or their methallyl derivatives with hydrogen sulfite in the presence of peroxo disulfates alone or in a mixture with other oxidation agents with a pH-value-range from 1.5 to 6.0 in a watery solution, whereby in light of the selection of the amount of hydrogen sulfite in combination with the amount peroxo disulfate different SO2--or SO3 - substituted sulfomethyl-pyrralidinium betaines are generated. The novel compounds are effective as specific tensides in a wide pH-range and can be extensively used as intermediary products.

We claim: 
     
       1. 3-sulfinatomethyl- and 3-sulfonatomethyl-4-sulfomethyl-pyrrolidinium betaines of Formula Ia and Ib ##STR51## wherein (A) R 1  is (a) hydrogen;   (b) selected from the group consisting of (bi) unsubstituted C 1  -C 22  alkyl,   (bii) CH 2  --CO--NH-alkyl, wherein alkyl is CH 3  to C 21  H 43 , and   (biii) CH(CO--NH-alkyl) 2 , wherein alkyl is CH 3  to C 21  H 43  ;     (c) 2-hydroxyethyl;   (d) (CH 2  --CH 2  --O) n  H with n=1 to 10;   (e) benzyl;   (f) --CH 2  --CH 2  --CH 2  --SO 3   -  ;   (g) ##STR52## (h) ##STR53## (B) R 2  is, independennt of R 1 , (a) hydrogen;   (b) selected from the group consisting of (bi) unsubstituted C 1  -C 22  alkyl;   (bii) CH 2  --CO--NH-alkyl, wherein alkyl is CH 3  to C 21  H 43  ; and   (biii) CH(CO--NH--alkyl) 2 , wherein alkyl is CH 3  to C 21  H 43  ;     (c) 2-hydroxyethyl or   (d) (CH 2  --CH 2  --O) n  H with n=1 to 10;   (C) R 1  and R 2  form together with the nitrogen atom a substituted hetereocyclic ring with 4 carbon atoms of the structure ##STR54## (D) R 3  and R 4  are hydrogen or methyl; (E) M+ is selected from the group consisting of Na, K, NH 4  and H; and   (F) X represents a whole number from 1 to 3.   
     
     
       2. Process for the preparation of 3-sulfinatomethyl- and 3-sulfonatomethyl-4-sulfomethyl-pyrrolidinium betaines of Formula Ia and Ib according to claim 1 by reacting diallyl ammonium salts of Formula II ##STR55## wherein (A) R o  is (a) hydrogen   (b) selected from the group consisting of (bi) unsubstituted C 1  -C 22  alkyl;   (bii) CH 2  --CO--NH-alkyl, wherein alkyl is CH 3  to C 21  H 43 , and   (biii) CH(CO--NH-alkyl) 2 , wherein alkyl is CH 3  to C 21  H 43  ;   (c) 2-hydroxyethyl;   (d) (CH 2  --CH 2  --O) n  H with n=1 to 10;   (e) benzyl;     (B) R 2  is, independent of R o , (a) hydrogen;   (b) selected from the group consisting of (bi) unsubstituted C 1  -C 22  alkyl,   (bii) CH 2  --CO--NH-alkyl, wherein alkyl is CH 3  to C 21  H 43 , and   (biii) CH(CO--NH-alkyl) 2 , wherein alkyl is CH 3  to C 21  H 43  ;     (c) 2-hydroxyethyl;   (d) (CH 2  --CH 2  O) n  H with n=1 to 10;     (C) R 3  and R 4  are hydrogen or methyl; and   (D) Y -   is selected from the group consisting of chloride, bromide, methosulfate and sulfate; or by reacting triallyl ammonium salts of Formula ##STR56## wherein (A) R 2  is (a) hydrogen;   (b) selected from the group consisting of (bi) unsubstituted C 1  -C 22  alkyl,   (bii) CH 2  --CO--NH-alkyl, wherein alkyl is CH 3  to C 21  H 43 , and   (biii) CH(CO--NH-alkyl) 2 , wherein alkyl is CH 3  to C 21  H 43  ;   (c) 2-hydroxyethyl;   (d) (CH 2  --CH 2  O) n  H with n=1 to 10, or (e) allyl,       (C) R 3  and R 4  are hydrogen or methyl; and   (D) Y 31   is selected from the group consisting of chloride, bromide, methosulfate and sulfate; with hydrogen sulfite salts having the formula MHSO 3 , wherein M is Na, K or NH 4 , in the presence of peroxo disulfate salt having the formula M 2  S 2  O 8 , wherein M is Na, K or NH 4 , or inthe presence of a mixture of a peroxo disulfate salt with other oxidation means having the formula Cl 2 , MClO, MClO 3 , MBrO 3 , H 2  O 2 , or O 2 , wherein M is Na, K or NH 4 , in the pH-range from 1.5 to 6 and in an aqueous phase.   
     
     
       3. Process for the preparation of 3-sulfinatomethyl-4-sulfomethyl-pyrrolidinium betaines of Formula Ia according to claim 2: (a) by reacting diallyl ammonium salts of Formula II with the double molar amount of hydrogen sulfite salts in the presence of a catalytic amount of peroxo disulfate salt in the pH-range of from 2 to 4;   (b) by reacting triallyl ammonium salts of Formula III with the triple molar amount of hydrogen sulfite salts in the presence of a catalytic amount of peroxo disulfate salt alone or in combination with a simultaneous or subsequent effect of oxygen in air in the pH-range from 2.5 to 6; or   (c) by reacting triallyl ammonium salts of Formula III with at least the quadruple molar amount of hydrogen sulfite salts in the presence of catalytic amount of a peroxo disulfate salt in the pH-range from 1.5 to 2.5.   
     
     
       4. The process of claim 3, wherein said reacting with the triple molar amount of hydrogen sulfite salts is effected with a pH-range between 4.0 and 5.5. 
     
     
       5. Process for the preparation of 3-sulfonatomethyl-4-sulfomethyl-pyrrolidinium betaines of Formula Ib according to claim 2: (a) by reacting diallyl ammonium salts of Formula II with the double molar amount of hydrogen sulfite salts and one molar amount of peroxo disulfate salts alone or in combination with simultaneous presence of a mixture of peroxo disulfate salts with other oxidation means with a total of two oxidation equivalents in the pH-range from 2 to 4;   (b) by reacting triallyl ammonium salts of Formula III with the triple molar amount of hydrogen sulfite salts and one molar amount of peroxo disulfate salts alone or in combination with simultaneous presence of a mixture of peroxo disulfate salts with other oxidation means with a total of four oxidation equivalents in the pH-range from 1.5 to 2.5; or   (c) by reacting triallyl ammonium salts of Formula III with the quadruple molar amount of hydrogen sulfite salts and the double molar amount of peroxo disulfate salts or in combination with simultaneous presence of a mixture of peroxo disulfate salts with other oxidation means with a total of four oxidation equivalents in the pH-range from 1.5 to 2.5.   
     
     
       6. The process of claim 5, wherein said reacting with the triple molar amount of hydrogen sulfite salts is effected with a pH-range between 4.0 and 5.5. 
     
     
       7. Process for the preparation of 3-sulfinatomethyl- or 3-sulfonatomethyl-4-sulfomethyl-pyrrolidinium betaines of Formula Ia and Ib according to claim 2, wherein said oxidation means which are used in the mixture with peroxo disulfate salts are chlorine, chlorate, bromate, hydrogen peroxide or oxygen in air.